CN102754032A - Photosensitive resin composition and photosensitive element using same, resist pattern formation method and printed circuit board manufacturing method - Google Patents

Photosensitive resin composition and photosensitive element using same, resist pattern formation method and printed circuit board manufacturing method Download PDF

Info

Publication number
CN102754032A
CN102754032A CN2010800631009A CN201080063100A CN102754032A CN 102754032 A CN102754032 A CN 102754032A CN 2010800631009 A CN2010800631009 A CN 2010800631009A CN 201080063100 A CN201080063100 A CN 201080063100A CN 102754032 A CN102754032 A CN 102754032A
Authority
CN
China
Prior art keywords
methyl
polymer combination
photosensitive polymer
formula
photo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2010800631009A
Other languages
Chinese (zh)
Other versions
CN102754032B (en
Inventor
味冈芳树
薄叶爱美
神尾贤治
石充
矶纯一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lishennoco Co ltd
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of CN102754032A publication Critical patent/CN102754032A/en
Application granted granted Critical
Publication of CN102754032B publication Critical patent/CN102754032B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
    • G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
    • G03F7/202—Masking pattern being obtained by thermal means, e.g. laser ablation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Optics & Photonics (AREA)
  • Polymerisation Methods In General (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

The disclosed photosensitive resin composition is used in the formation of a resist pattern by a direct-write method, and contains a binder polymer (A), a photopolymerisable compound (B) and a photopolymerisation initiator (C). The photopolymerisable compound (B) includes a compound represented by general formula (I). (In the formula R1 and R2 each independently represent a hydrogen atom or a methyl group and n represents an integer from 0-50.

Description

Photosensitive polymer combination and use its photosensitive element, the formation method of resist pattern and the manufacturing approach of printed-wiring board (PWB)
Technical field
The present invention relates to photosensitive polymer combination and use its photosensitive element, the formation method of resist pattern and the manufacturing approach of printed-wiring board (PWB).
Background technology
In the manufacturing field of printed-wiring board (PWB), as the anticorrosive additive material that uses in etching, the plating etc., photosensitive polymer combination is widely used.Photosensitive polymer combination process mostly have support membrane be formed at the layer that forms with photosensitive polymer combination on this support membrane (below be called " photo-sensitive resin ".) photosensitive element and use.
When using photosensitive element to make printed-wiring board (PWB), for example as following, operate and the manufacturing printed-wiring board (PWB).At first, with the photo-sensitive resin of photosensitive element range upon range of (lamination) (range upon range of operation) on substrate.Next, according to circumstances peel off remove support membrane after, to the established part of photo-sensitive resin irradiation active ray, make this established part exposure, solidify (exposure process).Then, the part (unexposed, uncured portion) beyond this established part is removed (developments) from the substrate, thus the resist pattern (developing procedure) that formation is made up of the solidfied material of photosensitive polymer combination on substrate.Next, be mask with this resist pattern, the substrate that has formed resist pattern is implemented etching or plating processing, form circuitous pattern, remove resist pattern (circuitous pattern formation operation) from strippable substrate at last.Be manufactured on the printed-wiring board (PWB) that has formed circuitous pattern on the substrate thus.
In above-mentioned exposure process, used the mask exposure method of shining active ray through mask film with figure in the past.As the light source of active ray, use carbon arc lamp, mercury vapour arc lamp, ultrahigh pressure mercury lamp, high-pressure sodium lamp, xenon lamp etc. effectively to radiate ultraviolet light source.
In recent years, the method for aforementioned mask exposure method instead, do not use mask film and be to use numerical data, with the direct picture of image shape direct irradiation active ray practicability.As the light source that uses in the direct picture, can use YAG laser, semiconductor laser etc. from aspects such as security, the property handled, proposed to use the technology of long-life, the high gallium nitride based blue laser of exporting etc. recently.
And then, along with the height of printed-wiring board (PWB) becomes more meticulous, densification, adopted the direct picture that is called as DLP (Digital Light Processing, digital light is handled) exposure method that can form than finer in the past figure.Usually, using with the bluish violet semiconductor laser in the DLP exposure method is the active ray of 390～430nm as the wavelength of light source.In addition, also use a small amount of many kinds mainly can tackle in the general printed-wiring board (PWB), used with YAG laser and be the wavelength of light source exposure method as the polygonal mirror multiple beam (polygon multi-beam) of 355nm.
On the other hand, in the above-mentioned developing procedure, as the developer solution that is used for removing from substrate the unexposed portion of photo-sensitive resin, from the position of environment property and security, alkaline developers such as aqueous sodium carbonate, sodium bicarbonate aqueous solution have become main flow.The unexposed portion of photo-sensitive resin is pressed and is removed from substrate through the development that utilizes these developer solutions, the spray of washing.Therefore, to photosensitive polymer combination require to have after the exposure because of develop, the spray of washing presses the lid hole reliability (hole covering character) of damaged excellence.
As the photosensitive polymer combination that in mask exposure method in the past, has excellent lid hole reliability, proposed to contain the photosensitive polymer combination (reference example such as patent documentation 1 and 2) of two senses or trifunctional monomer.
The prior art document
Patent documentation
Patent documentation 1: No. 3199600 communiques of Jap.P.
Patent documentation 2: No. 3251446 communiques of Jap.P.
Summary of the invention
The problem that invention will solve
Yet,, in above-mentioned direct picture, do not have sufficient lid hole reliability though the above-mentioned photosensitive polymer combination that contains two senses or trifunctional monomer has excellent lid hole reliability in mask exposure method in the past.
Therefore, the object of the present invention is to provide the photosensitive polymer combination that when having carried out exposure with direct picture, has had excellent lid hole reliability.In addition, purpose is to provide the photosensitive element that has used above-mentioned photosensitive polymer combination, the formation method of resist pattern and the manufacturing approach of printed-wiring board (PWB).
The method of dealing with problems
The inventor etc. further investigate in order to address the above problem repeatedly; The compound that the result finds to have the particular chemical structure through use is as the optical polymerism compound; Can be provided at direct picture and carry out having the photosensitive polymer combination of excellent lid hole reliability when making public, thereby accomplish the present invention.
Promptly; The present invention is a kind of photosensitive polymer combination; Contain (A) binder polymer, (B) optical polymerism compound and (C) Photoepolymerizationinitiater initiater; Above-mentioned (B) optical polymerism compound contains the compound shown in the formula (I), and said photosensitive polymer combination uses in the formation of the resist pattern that utilizes direct picture.Through using the compound shown in the formula (I) as above-mentioned (B) optical polymerism compound, the susceptibility of photosensitive polymer combination of the present invention is good, when having carried out exposure with direct picture, has excellent lid hole reliability.
[Chemical formula 1]
Figure BDA00001971376000031
In the above-mentioned general formula (I), R 1And R 2Represent hydrogen atom or methyl independently of one another, n representes 0～50 integer.The viewpoint that reliability further improves from the lid hole, n is preferably 4～25 integer.
From the viewpoint that fissility further improves, above-mentioned (B) optical polymerism compound preferably further contains the compound shown in the formula (II).
[Chemical formula 2]
Figure BDA00001971376000032
In the above-mentioned general formula (II), R 3Expression hydrogen atom or methyl, R 4The expression carbon number is 9 alkyl, and m representes 0～20 integer.The viewpoint that reliability further improves from the lid hole, m is preferably 4～8 integer.
From the viewpoint that susceptibility further improves, above-mentioned (C) Photoepolymerizationinitiater initiater preferably contains the compound shown in compound shown in the formula (III) and/or the formula (IV).
[chemical formula 3]
Figure BDA00001971376000033
In the above-mentioned general formula (III), R 5The expression carbon number is 2～20 alkylidene, oxa-two alkylidenes or sulfo-two alkylidenes.
[chemical formula 4]
Figure BDA00001971376000041
In the above-mentioned general formula (IV), R 6Expression can have substituent 1 valency aromatic series base.
In addition, the present invention relates to a kind of photosensitive element with support membrane and the photo-sensitive resin that is formed at the above-mentioned photosensitive polymer combination formation of usefulness on this support membrane.
In addition, the present invention relates to a kind of formation method of resist pattern, it has: the range upon range of operation of using the photo-sensitive resin of above-mentioned photosensitive polymer combination formation in the substrate laminated; Above-mentioned photo-sensitive resin is made the exposure process of exposure portion curing with image shape irradiation active ray through direct picture; Thereby form the developing procedure of the resist pattern that the solidfied material by photosensitive polymer combination constitutes at substrate with the unexposed portion of removing above-mentioned photo-sensitive resin from substrate.
In addition, the present invention relates to a kind of manufacturing approach of printed-wiring board (PWB), the substrate that contains be formed with resist pattern through said method carries out etching or plating.
The effect of invention
According to the present invention, the photosensitive polymer combination that has excellent susceptibility, when having carried out exposure with direct picture, had excellent lid hole reliability can be provided.In addition, the photosensitive element that has used above-mentioned photosensitive polymer combination, the formation method of resist pattern and the manufacturing approach of printed-wiring board (PWB) are provided, thereby can make printed-wiring board (PWB) with the meticulous circuitous pattern of height.
Description of drawings
Fig. 1 is the end view drawing of an embodiment of expression photosensitive element of the present invention.
Fig. 2 covers the hole of using in the evaluation of the hole reliability number that breaks to measure the vertical views with substrate.
Embodiment
Below, the limit specifies the mode that is used for embodiment of the present invention with reference to the accompanying drawing limit as required.But the present invention is not limited by following embodiment.In addition, identical element has same-sign in the accompanying drawing, omits repeat specification.In addition, the dimensional ratios of accompanying drawing is not limited by illustrated ratio." (methyl) acrylic acid " in this instructions is meant " acrylic acid " and " methacrylic acid " corresponding with it; " (methyl) acrylic ester " is meant " acrylic ester " and " methacrylate " corresponding with it, and " (methyl) acryloyl group " is meant " acryloyl group " and " methacryl " corresponding with it.
(photosensitive polymer combination)
The photosensitive polymer combination of this embodiment be contain (A) binder polymer (below be also referred to as " (A) composition ".), (B) optical polymerism compound (below be also referred to as " (B) composition ".) and (C) Photoepolymerizationinitiater initiater (below be also referred to as " (C) composition ".) and the photosensitive polymer combination that in the formation of the resist pattern that utilizes direct picture, uses.Here, " directly picture " is meant: do not use mask film etc., and be based on numerical data, to photo-sensitive resin with image shape irradiating laser light isoreactivity light, thereby the figure of hope directly is depicted in the exposure method on the photo-sensitive resin.
< (B) composition: optical polymerism compound >
It is the optical polymerism compound as (B) composition that the photosensitive polymer combination of this embodiment contains the compound shown in the formula (I).Thus, the photosensitive polymer combination of this embodiment has excellent lid hole reliability when having carried out exposure through direct picture.Here; " lid hole reliability " be meant after the exposure because develop, the spray of washing presses and damaged character (hole covering character), the evaluation of lid hole reliability can be measured and measures abnormity with substrate and cover hole rupture rate (%) and carry out through using the hole shown in Figure 2 number that breaks.
[chemical formula 5]
In the compound shown in the above-mentioned general formula (I), R 1And R 2Represent hydrogen atom or methyl independently of one another.From the viewpoint that anti-development fluidity improves, R 1And R 2Be preferably methyl.In addition, in the compound shown in the above-mentioned general formula (I), n representes 0～50 integer.The viewpoint that reliability further improves from the lid hole, said n is preferably 4～25 integer, and more preferably 9～24 integer further is preferably 9～14 integer.
As the compound shown in the above-mentioned general formula (I), can enumerate out two (methyl) acrylic anhydride (n=0) and (gathering) ethylene glycol bisthioglycolate (methyl) acrylic ester (n=1～50).(gathering) ethylene glycol bisthioglycolate (methyl) acrylic ester can obtain through making (methyl) acrylic acid and (gathering) glycol reaction.As the compound shown in the commercial above-mentioned general formula (I) that can obtain, can enumerate out 9G, 14G, 23G polyethylene glycol dimethacrylates such as (being Xin Zhong village chemical industry (strain) manufacturing, trade name).
From the excellent viewpoint of the balance of susceptibility and resolution, be benchmark with the gross mass of (B) composition, the content of the compound shown in the above-mentioned general formula (I) is preferably 5～90 quality %.From the excellent viewpoint of lid hole reliability, more than the preferred 5 quality % of above-mentioned content, more preferably more than the 10 quality %, further more than the preferred 15 quality %, more than the preferred especially 20 quality %.In addition, from the excellent viewpoint of filming property, below the preferred 90 quality % of above-mentioned content, more preferably below the 70 quality %, further below the preferred 50 quality %, below the preferred especially 40 quality %.
The photosensitive polymer combination of this embodiment can also contain (B) composition beyond the compound shown in the above-mentioned general formula (I).As these (B) compositions, if having ethene property unsaturated link, can photo-crosslinking, just not special restriction, the compound (B1)～(B5) below for example can enumerating out.These compounds can use separately or two or more combinations are used.
(B1) bisphenol-A is two (methyl) acrylate compounds
(B2) has the compound of 1 ethene property unsaturated link
(B3) make α, beta-unsaturated carboxylic acid and polyol reaction and compound
(B4) make α, the compound that beta-unsaturated carboxylic acid gets with containing the glycidyl compound reaction
(B5) have the carbamate monomers such as (methyl) acrylate compounds of amino-formate bond
Wherein, from the viewpoint of susceptibility and excellent in resolution, (B) preferably to contain bisphenol-A be two (methyl) acrylate compounds (B1) to composition.As (B1); For example can enumerate out 2; Two (4-((methyl) acryloyl-oxy Quito ethoxy) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloyl-oxy Quito propoxyl group) phenyl) propane and 2 of 2-, two (4-(the many propoxyl group of (methyl) acryloyl-oxy Quito ethoxy) phenyl) propane of 2-.
As above-mentioned 2; Two (4-((methyl) acryloyl-oxy Quito ethoxy) phenyl) propane of 2-; For example can enumerate out 2; Two (4-((methyl) acryloxy diethoxy) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy triethoxy) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy tetraethoxy) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy five ethoxys) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy six ethoxys) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy seven ethoxys) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy eight ethoxys) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy nine ethoxys) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy ten ethoxys) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy 11 ethoxys) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy ten diethoxies) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy ten triethoxies) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy ten tetraethoxies) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy 15 ethoxys) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy 16 ethoxys) phenyl) propane of 2-.With regard to 2; Two (4-(the methacryloxy five ethoxys) phenyl) propane of 2-can commercially obtain BPE-500 (Xin Zhong village chemical industry (strain) manufacturing, trade name); With regard to 2; Two (4-(the methacryloxy 15 ethoxys) phenyl) propane of 2-can the commercial BPE-1300 of acquisition (Xin Zhong village chemical industry (strain) is made, trade name).These materials can use separately, perhaps two or more combinations are used.
As above-mentioned 2; Two (4-((methyl) acryloyl-oxy Quito propoxyl group) phenyl) propane of 2-; For example can enumerate out 2; Two (4-((methyl) acryloxy dipropoxy) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy tripropoxy) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy four propoxyl group) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy five propoxyl group) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy six propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy seven propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy eight propoxyl group) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy nine propoxyl group) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy ten propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy 11 propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy ten dipropoxies) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy ten tripropoxies) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy 14 propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy 15 propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy 16 propoxyl group) phenyl) propane of 2-.These materials can use separately, perhaps two or more combinations are used.
As above-mentioned 2; Two (4-(the many propoxyl group of (methyl) acryloyl-oxy Quito ethoxy) phenyl) propane of 2-; For example can enumerate out 2; Two (4-((methyl) acryloxy diethoxy eight propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy tetraethoxy four propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy six ethoxys six propoxyl group) phenyl) propane of 2-.These materials can use separately, perhaps two or more combinations are used.
When (B) composition contains bisphenol-A and is two (methyl) acrylate compounds (B1), be benchmark with the gross mass of (B) composition, its content is preferably 20～80 quality %, more preferably 30～70 quality %.
In addition, from the excellent viewpoint of lid hole reliability, (B) composition preferably contains the compound (B2) that has 1 ethene property unsaturated link in the molecule.As (B2), can enumerate out Nonylphenoxy system (methyl) acrylate compounds shown in the formula (II), γ-chloro-beta-hydroxy propyl group-β '-(methyl) acryloxy ethyl-phthalic ester, beta-hydroxy ethyl-β '-(methyl) acryloxy ethyl-phthalic ester, beta-hydroxy propyl group-β '-(methyl) acryloxy ethyl-phthalic ester etc.Wherein, preferably contain Nonylphenoxy system (methyl) acrylate compounds shown in the formula (II).
[chemical formula 6]
Figure BDA00001971376000081
In the compound shown in the above-mentioned general formula (II), R 3Expression hydrogen atom or methyl.From the viewpoint that the development fluidity improves, R 3Be preferably hydrogen atom.R 4The expression carbon number is 9 alkyl.In addition, in the compound shown in the above-mentioned general formula (II), m representes 0～20 integer.The viewpoint that reliability further improves from the lid hole, above-mentioned m is preferably 4～15 integer, and more preferably 4～10 integer further is preferably 4～8 integer.
As the compound shown in the above-mentioned general formula (II), can enumerate out Nonylphenoxy (methyl) acrylic ester (m=0) and Nonylphenoxy (gathering) monoethylene glycol (methyl) acrylic ester (m=1～20).Nonylphenoxy (gathering) monoethylene glycol (methyl) acrylic ester can obtain through making (gathering) monoethylene glycol, nonyl phenol and the reaction of (methyl) acrylic acid.As Nonylphenoxy (gathering) monoethylene glycol (methyl) acrylic ester, can enumerate out Nonylphenoxy TEG (methyl) acrylic ester, Nonylphenoxy eight monoethylene glycol (methyl) acrylic ester etc.As the compound shown in the commercial above-mentioned general formula (II) that can obtain, can enumerate out FA-314A, FA-318A Nonylphenoxy (gathering) EDIAs such as (are Hitachi Chemical Co., Ltd. and make trade name).
From the excellent viewpoint of the balance of susceptibility and resolution, be benchmark with the gross mass of (B) composition, the content of the compound shown in the above-mentioned general formula (II) is preferably 5～90 quality %.From the excellent viewpoint of lid hole reliability, more than the preferred 5 quality % of above-mentioned content, more preferably more than the 10 quality %, further more than the preferred 15 quality %, more than the preferred especially 20 quality %.In addition, from the excellent viewpoint of filming property, below the preferred 90 quality % of above-mentioned content, more preferably below the 70 quality %, further below the preferred 50 quality %, below the preferred especially 40 quality %.
As the above-mentioned α that makes; Beta-unsaturated carboxylic acid and polyol reaction and compound (B3); Can enumerate out oxygen propylidene (oxypropylene group) number for example and be 2～14 polypropylene glycol two (methyl) acrylic ester, trimethylolpropane two (methyl) acrylic ester, trimethylolpropane tris (methyl) acrylic ester, EO modification trimethylolpropane tris (methyl) acrylic ester (the repeating to add up to 1～5 of oxygen ethylidene), PO modification trimethylolpropane tris (methyl) acrylic ester, EO, PO modification trimethylolpropane tris (methyl) acrylic ester, tetramethylol methane three (methyl) acrylic ester, tetramethylol methane four (methyl) acrylic ester, dipentaerythritol five (methyl) acrylic ester, dipentaerythritol six (methyl) acrylic ester.These materials can use separately, or above combination in 2 is used.Here; " EO modification " is meant the compound (having carried out the compound of polyoxyethyleneization) of the block structure with (gathering) oxygen ethylene chain; " PO modification " is meant the compound (having carried out the compound of polyoxypropyleneization) of the block structure with (gathering) oxypropylene chain, and " EOPO modification " is meant the compound (having carried out the compound of polyoxyethyleneization and polyoxypropyleneization) of the block structure with (gathering) oxygen ethylene chain and (gathering) oxypropylene chain.These materials can use separately, perhaps two or more combinations are used.
As above-mentioned carbamate monomer (B5); Can enumerate out (methyl) acrylic monomer and IPDI, 2 that β position for example has hydroxyl; 6-toluene diisocyanate, 2; 4-toluene diisocyanate and 1, the addition reaction of diisocyanate cpds such as 6-hexamethylene diisocyanate; Three ((methyl) acryloxy TEG isocyanates) hexa-methylene isocyanuric acid ester; EO modified amido formic ether two (methyl) acrylic ester; EO, PO modified amido formic ether two (methyl) acrylic ester etc.As EO modified amido formic ether two (methyl) acrylic ester, can enumerate out for example Xin Zhong village chemical industry (strain) manufacturing, trade name UA-11 etc.In addition, as EO, PO modified amido formic ether two (methyl) acrylic ester can be enumerated out for example Xin Zhong village chemical industry (strain) manufacturing, trade name UA-13 etc.In addition, as three ((methyl) acryloxy TEG isocyanates) hexa-methylene isocyanuric acid ester, can enumerate out for example Xin Zhong village chemical industry (strain) manufacturing, trade name UA-21 etc.Wherein, from the viewpoint of further raising lid hole reliability, UA-21 is preferably 5～25 weight %, more preferably 7～15 weight %.These materials can use separately, perhaps two or more combinations are used.
With respect to (A) composition and (B) total amount 100 mass parts of composition, (B) content of composition (optical polymerism compound) preferably is made as 20～60 mass parts.From improving the viewpoint of susceptibility and resolution, (B) content of composition is preferably more than 20 mass parts, more preferably more than 25 mass parts, further is preferably more than 30 mass parts.From the viewpoint of giving film property with solidify after the excellent viewpoint of resist shape, (B) content of composition is preferably below 60 mass parts, more preferably below 55 mass parts, further is preferably below 50 mass parts.
< (A) composition: binder polymer >
As (A) composition is binder polymer; As long as it is solvable and can form epithelium in aqueous alkali; Just not special restriction, for example can enumerating out, acrylic resin, phenylethylene resin series, epoxy are that resin, acid amides are that resin, acid amides epoxy are that resin, alkyd are resin and phenol resin.Wherein, from the position of alkali-developable, preferred acrylic resin.These materials can use separately, perhaps two or more combinations are used.
(A) composition can be made through for example making polymerizable monomer (monomer) carry out free radical polymerization.As polymerizable monomer, for example can enumerate out: styrene; AMS, vinyltoluene etc. have carried out substituted styrene derivative that can polymerization at alpha-position or aromatic ring; Acrylic amides such as DAAM; Vinyl cyanide; The ethers of vinyl alcohol such as vinyl-n-butyl ether; (methyl) alkyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid tetrahydrofuran ester, (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) glycidyl acrylate, (methyl) acrylic acid 2; 2; 2-trifluoro ethyl ester, (methyl) acrylic acid 2; 2,3, (methyl) acrylic ester such as 3-tetrafluoro propyl ester; (methyl) acrylic acid derivatives such as (methyl) acrylic acid, α-bromine (methyl) acrylic acid, α-chlorine (methyl) acrylic acid, β-furyl (methyl) acrylic acid, β-styryl (methyl) acrylic acid; Maleic acid derivatives such as maleic acid, maleic anhydride, monomethyl maleate, ethyl maleate, maleic acid list isopropyl ester; Organic acid derivatives such as fumaric acid, cinnamic acid, alpha-cyano cinnamic acid, itaconic acid, crotonic acid, propiolic acid.These materials can use separately, perhaps two or more combinations are used.
As above-mentioned (methyl) alkyl acrylate, can enumerate out the compound shown in the formula (V).
[chemical formula 7]
Figure BDA00001971376000101
In the above-mentioned general formula (V), R 7Expression hydrogen atom or methyl, R 8The expression carbon number is 1～12 alkyl.
As the R in the above-mentioned general formula (V) 8Shown carbon number is 1～12 alkyl, can enumerate out for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl and their constitutional isomer.
As the compound shown in the above-mentioned general formula (V), for example can enumerate out (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid heptyl ester, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) acrylic acid undecyl ester, (methyl) dodecylacrylate.These materials can use separately, perhaps two or more combinations are used.
In addition,, can also enumerate out in the compound shown in the above-mentioned general formula (V) as above-mentioned (methyl) alkyl acrylate, alkyl replaced by hydroxyl, epoxy radicals, halogen etc. and compound.
From the position of alkali-developable, (A) composition preferably contains carboxyl.(A) composition that contains carboxyl can be made through making the polymerizable monomer that for example has carboxyl and other polymerizable monomer carry out free radical polymerization.As above-mentioned polymerizable monomer with carboxyl, preferred (methyl) acrylic acid, wherein more preferably methacrylic acid.
From the position of the balance of alkali-developable and developer solution patience, be benchmark with the gross mass of (A) composition, (A) carboxyl-content of composition (having the ratio of the polymerizable monomer of carboxyl with respect to the whole polymerizable monomers that use) is preferably 12～50 quality %.From the excellent viewpoint of alkali-developable, be preferably more than the 12 quality %, more preferably more than the 15 quality %.In addition,, be preferably below the 50 quality %, more preferably below the 40 quality %, further be preferably below the 30 weight %, be preferably especially below the 25 quality % from the excellent viewpoint of developer solution patience.
From the position of adaptation and peel property, (A) composition preferably contains styrene or styrene derivative as polymerizable monomer.From making all good position of adaptation and peel property; Gross mass with (A) composition is a benchmark, and its content when being copolymer composition with above-mentioned styrene or styrene derivative (styrene or styrene derivative are with respect to the ratio of the whole polymerizable monomers that use) preferably contains 0.1～30 quality %.From the excellent viewpoint of adaptation, be preferably more than the 0.1 quality %, more preferably more than the 1 quality %, further be preferably more than the 1.5 quality %.In addition,, be preferably below the 30 quality %, more preferably below the 28 quality %, further be preferably below the 27 quality % from the excellent viewpoint of fissility.
These (A) compositions (binder polymer) can use separately, perhaps make up two or more and use.And binder polymer when using two or more as combination can be enumerated out the two or more binder polymer of the two or more binder polymer that for example is made up of different copolymer compositions, different weight-average molecular weight, the two or more binder polymer of different dispersion degree etc.
From the position of the balance of anti-development fluidity and alkali-developable, (A) weight-average molecular weight of composition is preferably 20,000～300, and 000.From the excellent viewpoint of anti-development fluidity, be preferably more than 20,000, more preferably more than 40,000, further be preferably more than 50,000.From the excellent viewpoint of alkali-developable, be preferably below 150,000, more preferably below 120,000.What explain is, the weight-average molecular weight in this instructions is the value of utilizing gel permeation chromatography, converting through the calibration curve that uses polystyrene standard to make.
With respect to (A) composition and (B) total amount 100 mass parts of composition, (A) content of composition preferably is made as 40～80 mass parts.From giving the viewpoint of film property, be preferably more than 40 mass parts, more preferably more than 45 mass parts, further be preferably more than 50 mass parts.In addition,, be preferably below 80 mass parts, more preferably below 75 mass parts, further be preferably below 70 mass parts from the viewpoint of susceptibility and excellent in resolution.
< (C) composition: Photoepolymerizationinitiater initiater >
Photoepolymerizationinitiater initiater as (C) composition preferably contains the compound shown in compound shown in the formula (III) and/or the formula (IV).
[chemical formula 8]
In the compound shown in the above-mentioned general formula (III), R 5The expression carbon number is 2～20 alkylidene, oxa-two alkylidenes or sulfo-two alkylidenes.From making the better position of susceptibility and resolution, (C) composition preferably contains R 5Be that carbon number is that the compound (for example (strain) ADEKA makes, trade name " N-1717 ") of 7 alkylidene is as the compound shown in the above-mentioned general formula (III).
When (C) composition contains the compound shown in the above-mentioned general formula (IV); Position from the balance of susceptibility and resolution; With respect to (A) composition and (B) total amount 100 mass parts of composition; Its content is preferably 0.01～20 weight portion, and more preferably 0.1～10 weight portion further is preferably 0.2～5 weight portion.If it contains quantity not sufficient 0.01 weight portion, then there is the tendency that can't obtain sufficient susceptibility, when surpassing 20 weight portions, the resist shape is trapezoidal, has the tendency that can't obtain sufficient adaptation and resolution.
[chemical formula 9]
Figure BDA00001971376000131
In the compound shown in the above-mentioned general formula (IV), R 6Expression can have substituent 1 valency aromatic series base.From making the better position of adaptation and resolution, (C) composition preferably contains R 6For the compound of phenyl (for example Nippon Steel's chemistry (strain) is made, trade name " 9-PA ") as the compound shown in the above-mentioned general formula (IV).In addition, from making the better position of susceptibility, (C) composition preferably contains R 6For the compound of the phenyl that replaced by alkyl, halogen atom etc. as the compound shown in the above-mentioned general formula (IV).As such compound, can enumerate out R 6Compound (for example the powerful electronics new material of Changzhou company limited makes trade name " TR-PAD 102 ", " TR-PAD 103 ", " TR-PAD 104 ", " TR-PAD 105 ") for p-methylphenyl, a tolyl, o-tolyl, rubigan.
When (C) composition contains the compound shown in the above-mentioned general formula (IV); Position from the balance of susceptibility and resolution; With respect to (A) composition and (B) total amount 100 mass parts of composition; Its content is preferably 0.01～10 weight portion, and more preferably 0.05～5 weight portion further is preferably 0.1～3 weight portion.If this contains quantity not sufficient 0.01 weight portion, then have the tendency that can't obtain sufficient susceptibility, when surpassing 10 weight portions, the resist shape is trapezoidal, has the tendency that can't obtain sufficient adaptation and resolution.
Compound shown in compound shown in the above-mentioned general formula (III) and the above-mentioned general formula (IV) both can use separately also can make up use, can also compound shown in the above-mentioned general formula (III) more than 2 kinds or the combination of the compound shown in the above-mentioned general formula (IV) be used.
As (C) composition (Photoepolymerizationinitiater initiater) except that the compound shown in compound shown in the above-mentioned general formula (III) and the above-mentioned general formula (IV); Can enumerate out for example benzophenone, N; N '-tetramethyl-4; 4 '-diaminobenzophenone (Michler's keton), N; N '-tetraethyl-4,4 '-diaminobenzophenone, 4-methoxyl-4 '-dimethylamino benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1 and 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-aromatic ketones such as 2-morpholino-acetone-1; 2-EAQ, phenanthrenequione, 2-tert-butyl group anthraquinone, prestox anthraquinone, 1; 2-benzo anthraquinone, 2,3-benzo anthraquinone, 2-phenyl anthraquinone, 2,3-diphenyl anthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1; 4-naphthoquinones, 9; 10-phenanthrenequione, 2-methyl 1,4-naphthoquinones and 2, quinones such as 3-dimethyl anthraquinone; Benzoin ether compounds such as benzoin methyl ether, benzoin ethylether and benzoin phenyl ether; Benzoin compounds such as benzoin, methylbenzene acyloin and ethylbenzene acyloin; Benzil derivants such as benzil dimethyl ketal; 9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 9,10-dipropoxy anthracene, 9,10-dibutoxy anthracene and 9,10-two amoxy anthracenes etc. replace the anthracene class; 2-(Chloro-O-Phenyl)-4; 5-diphenyl-imidazole dimer, 2-(Chloro-O-Phenyl)-4,5-two (methoxyphenyl) imidazoles dimer, 2-(adjacent fluorophenyl)-4,5-diphenyl-imidazole dimer, 2-(o-methoxyphenyl)-4; 5-diphenyl-imidazole dimer and 2-(p-methoxyphenyl)-4; 5-diphenyl-imidazole dimer etc. 2,4,5-triarylimidazoles dimer; Coumarin series compounds 、 oxazole based compound, pyrazoline based compound.In addition, 22,4, the substituting group of the aryl of 5-triarylimidazoles can be identical and the compound of symmetry is provided, also can be different and asymmetrical compound is provided.In addition, also can as the combination of diethyl thioxanthone and dimethylamino benzoic acid, thioxanthones based compound and tertiary amine compound be made up.These materials can use separately or two or more combinations are used.
With respect to (A) composition and (B) total amount 100 weight portions of composition, (C) content of composition is preferably 0.01～20 weight portion, and more preferably 0.1～10 weight portion is preferably 0.2～5 weight portion especially.When the content of (C) composition was this scope, the susceptibility of photosensitive polymer combination was better with inner photo-curable.
< other composition >
And then the photosensitive polymer combination of this embodiment can be as required contains dyestuffs such as the gorgeous indigo plant of peacock green, Victoria about each 0.01～20 weight portion, bright green, methyl violet with respect to (A) composition and (B) total amount 100 weight portions of composition; Light developers such as LCV, diphenylamine, benzyl amine, triphenylamine, diethylaniline, o-chloraniline, trisbromomethyl sulfone; The heat colour developing prevents agent; Plastifier such as para toluene sulfonamide; Pigment; Filling agent; Foam-breaking agent; Fire retardant; The adaptation imparting agent; Levelling agent; Peel off promoter; Anti-oxidant; Spices; Preparation (imaging agent); Thermal cross-linking agent etc.These materials can use separately or two or more combinations are used.
(solution of photosensitive polymer combination)
Can the photosensitive polymer combination of this embodiment be dissolved in and process solid constituent in the organic solvent is that solution (coating fluid) about 30～60 quality % uses.As organic solvent, can enumerate out methyl alcohol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, dinethylformamide, propylene glycol monomethyl ether or their mixed solvent.
Above-mentioned coating fluid is coated on the surface of sheet metal etc. and dry, can forms the photosensitive polymer combination that uses this embodiment thus and the photo-sensitive resin that forms.As sheet metal, can enumerate iron-based alloys such as copper, copper series alloy, nickel, chromium, iron, stainless steel, preferably copper, copper series alloy, iron-based alloy etc.
The thickness of photo-sensitive resin is according to its purposes and difference is preferably counted about 1～100 μ m with dried thickness.Can also be with diaphragm be covered photo-sensitive resin and the surface sheet metal opposition side.As diaphragm, can enumerate out polymer films such as tygon, polypropylene etc.
(photosensitive element)
Fig. 1 representes an embodiment of photosensitive element of the present invention.The solution coat of above-mentioned photosensitive polymer combination is also dry on support membrane 2, thus the photo-sensitive resin 3 that uses above-mentioned photosensitive polymer combination and form can on support membrane 2, be formed.Next; Through with diaphragm 4 lining photo-sensitive resin 3 with surfaces support membrane 2 opposition sides, can obtain to possess support membrane 2, be layered in the photo-sensitive resin 3 on this support membrane 2 and be layered in the photosensitive element 1 of this embodiment of the diaphragm 4 on this photo-sensitive resin 3.Diaphragm 4 also can have.
As support membrane 2, the polymer film that can use polyester, polypropylene, tygon etc. such as polyethylene terephthalate to have thermotolerance and solvent resistance.The thickness of support membrane 2 (polymer film) is preferably 1～100 μ m, and more preferably 1～50 μ m further is preferably 1～30 μ m.
When this thickness less than 1 μ m, there are support membrane 2 crackly tendencies when peeling off support membrane 2, when surpassing 100 μ m, there is the tendency that is difficult to fully obtain resolution.
As diaphragm 4, preferably to the bonding force of photo-sensitive resin 3 the littler diaphragm of bonding force than 2 pairs of photo-sensitive resins 3 of support membrane, in addition, the preferred film of low flake.Here, " flake " is meant: through material is carried out heat fusing, mixing, extrude, when biaxial stretch-formed, casting etc. is made film, the foreign matter of material, melt, oxidative degradation thing etc. do not enter into film and the defective that causes.That is, " low flake " means that above-mentioned foreign matter in the film etc. is few.
Particularly, as diaphragm 4, the polymer film that can use polyester, polypropylene, tygon etc. such as polyethylene terephthalate to have thermotolerance and solvent resistance.As commercially available film, can enumerate out the Oji Paper manufactured ALPHAN MA ?410, E-200C; The polypropylene screen of SHIN-ETSU HANTOTAI's film manufactured etc.; The polyethylene terephthalate film of PS series such as the PS-25 of Supreme Being people's manufactured etc. etc.In addition, diaphragm 4 also can be the film identical with support membrane 2.
The thickness of diaphragm 4 is preferably 1～100 μ m, and more preferably 1～50 μ m further is preferably 1～30 μ m.When its thickness less than 1 μ m, exist photo-sensitive resin 3 diaphragm 4 crackly tendencies when diaphragm 4 range upon range of (lamination) is on substrate, when surpassing 100 μ m, have the inadequate tendency in cheapness property aspect.
The coating of the solution of photosensitive polymer combination on support membrane 2 can be coated with machine through roll coater, comma coating machine, intaglio plate coating machine, Kohler coater, mould, rod is coated with known method such as machine and carries out.
The drying of above-mentioned solution is preferably being carried out about 5～30 minutes under 70～150 ℃.The viewpoint of organic solvent diffusion from prevent subsequent handling, after the drying, the remaining organic solvent amount in the photo-sensitive resin preferably is made as below the 2 quality %.
The thickness of the photo-sensitive resin 3 in the photosensitive element 1 is according to purposes and difference is preferably counted 1～200 μ m with dried thickness, and more preferably 5～100 μ m further are preferably 10～50 μ m.When its thickness less than 1 μ m, exist and be difficult to the tendency that is coated with in the industry, when surpassing 200 μ m, there is the tendency that is difficult to fully to obtain the photo-curable bottom susceptibility and the resist.
Photosensitive element 1 can also further have middle layers such as cushion, adhesive linkage, light absorbing zone, gas-barrier layer etc.
The photosensitive element 1 that obtains can or be wound into the roller shape with sheet and take care of on the volume core.When being wound into the roller shape, the mode outside preferably becoming according to support membrane 2 is reeled.As the volume core, can enumerate out polyvinyl resin, acrylic resin, polystyrene resin, Corvic, ABS resin plastics such as (acrylonitrile-butadiene-styrene copolymers) etc.From the position of end face protection, at the end face of the photosensitive element roller of the roller shape that obtains like this end face dividing plate is set preferably, from the position on refractory limit, damp proof end face dividing plate is set preferably.With regard to bundling method, preferably wrap in the little black sheet of moisture-penetrability (black sheet) and pack.
(the formation method of resist pattern)
Can use above-mentioned photosensitive polymer combination to form resist pattern.The formation method of the resist pattern of this embodiment has: the photo-sensitive resin that (i) will use above-mentioned photosensitive polymer combination to form is layered in the range upon range of operation on the substrate; (ii) above-mentioned photo-sensitive resin is shone active ray through direct picture with the image shape, the exposure process that exposure portion is solidified; (iii) remove the unexposed portion of photo-sensitive resin, thereby on substrate, form the developing procedure of the resist pattern that the solidfied material by photosensitive polymer combination constitutes from substrate.
(i) range upon range of operation
At first, the photo-sensitive resin that the usability photosensitive resin composition is formed is layered on the substrate.As substrate, can use to have insulation course and the substrate that is formed at the conductor layer on this insulation course (circuit forms and uses substrate).
Photo-sensitive resin for example can be behind the diaphragm of removing above-mentioned photosensitive element 14 range upon range of on the substrate, and photo-sensitive resin 3 limits through limit heating photosensitive element 1 are crimped on it on aforesaid substrate carries out.Thus, can obtain by substrate and photo-sensitive resin 3 and support membrane 2 constitutes and they stack gradually the duplexer that forms.
From the position of adaptation and tracing ability, this range upon range of operation is preferably under reduced pressure carried out.Photo-sensitive resin during crimping and/or the heating of substrate are preferably carried out with 70～130 ℃ temperature, preferably with (1～10kgf/cm about 0.1～1.0MPa 2About) pressure carry out crimping, but the not special restriction of these conditions.In addition,, then there is no need in advance substrate to be carried out thermal pretreatment, but, also can carry out the thermal pretreatment of substrate in order further to improve stackability if photo-sensitive resin is heated to 70～130 ℃.
(ii) exposure process
Next, make public through direct picture.That is, do not use mask film, and be based on numerical data, to photo-sensitive resin 3 with image shape irradiating laser light isoreactivity light, thereby directly on photo-sensitive resin, describe the figure of hoping.At this moment, when 2 pairs of active rays of the support membrane on being present in photo-sensitive resin 3 are permeability, can shine active rays through support membrane 2, and when support membrane 2 is light-proofness, after removing support membrane 2, to photo-sensitive resin irradiation active ray.
As direct picture, can enumerate out laser and directly describe exposure method, DLP (Digital Light Processing) exposure method.Light source as active ray; Preferred YAG laser, semiconductor laser, gallium nitride based bluish violet color laser etc.; Also can use carbon arc lamp, mercury vapour arc lamp, ultrahigh pressure mercury lamp, high-pressure sodium lamp, xenon lamp etc. effectively to radiate ultraviolet light source, photoflood lamp bubble, sunlamp etc. effectively radiate the light source of visible light.
(iii) developing procedure
And then, remove the unexposed portion of photo-sensitive resin 3 from substrate, thereby on substrate, form the resist pattern that the solidfied material by photosensitive polymer combination constitutes.When having support membrane 2 on the photo-sensitive resin 3, remove remove (development) of carrying out unexposed portion behind the support membrane 2.Developing method comprises wet developing and dry process development, but the wet developing that is widely used.
Utilize under the situation of wet developing, use and the corresponding developer solution of photosensitive polymer combination, develop through known developing method.As developing method; Can enumerate the method for sening as an envoy to impregnation method, revolving submergence (puddle) mode of covering, spray pattern, brush, bat (slapping), scraping (scrapping), shake impregnating; From improving the viewpoint of resolution, optimal is the high-pressure fog mode.Also can the combination of the method more than 2 kinds in these be developed.
As developer solution, can enumerate alkaline water solution, water system developer solution, organic solvent is developer solution etc.
When alkaline aqueous solution uses as developer solution, safety and stable, operability is good.As the alkali of alkaline aqueous solution, can use the alkali hydroxides such as oxyhydroxide of lithium, sodium or potassium; Carbonic acid alkali such as the carbonate of lithium, sodium, potassium or ammonium or supercarbonate; Alkali metal phosphate such as potassium phosphate, sodium phosphate; Alkali metal pyrophosphate such as sodium pyrophosphate, potassium pyrophosphate etc.
As alkaline aqueous solution, the lean solution of the lean solution of the lean solution of preferred 0.1～5 quality % sodium carbonate, 0.1～5 quality % sal tartari, the lean solution of 0.1～5 quality % NaOH, 0.1～5 quality % sodium tetraborate etc.The pH of alkaline aqueous solution preferably is made as 9～11 scope, and its temperature can be regulated according to the alkali-developable of photo-sensitive resin.Can also sneak into surfactant, foam-breaking agent in the alkaline aqueous solution, be used to promote a small amount of organic solvent that develops etc.
The water system developer solution is the developer solution for being made up of water or alkaline aqueous solution and the organic solvent more than a kind for example.Here; As the alkali of alkaline aqueous solution, except that aforementioned substances, can also enumerate out for example borax, sodium metasilicate, TMAH, monoethanolamine, ethylenediamine, diethylene triamine, 2-amino-2-methylol-1; Ammediol, 1,3-diamino-propanol-2, morpholine etc.
The pH of water system developer solution preferably is made as as far as possible little in the scope that can fully develop, preferably is made as pH8～12, more preferably is made as pH9～10.
As the organic solvent that uses in the water system developer solution, can enumerate out acetone, ethyl acetate, have alkoxyethanol, ethanol, isopropyl alcohol, butanols, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether of the alkoxy of carbon number 1～4 etc.These materials can use separately or two or more combinations are used.The concentration of the organic solvent in the water system developer solution preferably is made as 2～90 quality % usually, and its temperature can be adjusted according to alkali-developable.Also can sneak into surfactant, foam-breaking agent etc. on a small quantity in the water system developer solution.
As organic solvent is developer solution, for example can enumerate out 1,1,1-trichloroethanes, N-Methyl pyrrolidone, N, organic solvents such as dinethylformamide, cyclohexanone, methyl isobutyl ketone, gamma-butyrolacton.On fire for preventing, preferably the scope with 1～20 quality % is added water in these organic solvents.
After removing unexposed portion, can also carry out heating or the 0.2～10J/cm about 60 ℃～250 ℃ as required 2About exposure, thereby resist pattern is further solidified.
(manufacturing approach of printed-wiring board (PWB))
Through the substrate that utilizes said method to form resist pattern is carried out etching or plating, can make printed-wiring board (PWB).The etching of substrate or plating are to be mask and the conductor layer of substrate etc. is carried out with the resist pattern that forms.
Etching solution when carrying out etching can be enumerated out copper chloride solution, ferric chloride solution, alkaline etching solution, hydrogen peroxide etching solution, from the good viewpoint of etching factor, and the preferred ferric chloride solution that uses among these etching solutions.
Method for plating when carrying out plating; Can enumerate out copper platings such as copper sulphate plating, cupric pyrophosphate plating; Scolding tin platings such as high evenly scolding tin (high-throw solder) plating; Watt is bathed nickel platings such as (nickelous sulfate-nickel chloride) plating, nickel sulfamic acid, golden platings such as hard gold plating, soft golden plating etc.
After etching or plating finished, resist pattern for example can be through peeling off than the more alkaline WS of alkaline aqueous solution that uses in developing.As this alkaline WS, can use for example 1～10 quality % sodium hydrate aqueous solution, 1～10 quality % potassium hydroxide aqueous solution etc.Wherein, preferably use 1～10 quality % sodium hydrate aqueous solution or potassium hydroxide aqueous solution, more preferably use 1～5 quality % sodium hydrate aqueous solution or potassium hydroxide aqueous solution.
As the mode of peeling off of resist pattern, can enumerate out impregnation method, spray pattern etc., these modes can be used separately also and can and use.In addition, the printed-wiring board (PWB) that has formed resist pattern both can be a multilayer printed circuit board, also can have the minor diameter through hole.
Embodiment
Below enumerate embodiment the present invention more specifically is described.But the present invention is not limited by following examples.
[(A) composition: binder polymer]
(preparation of solution a)
In the mixed liquor that is made up of the polymerizable monomer shown in the table 1 (comonomer, monomer), dissolving prepares " solution a " as the azoisobutyronitrile 0.8g of free radical reaction initiating agent.
[table 1]
Polymerizable monomer Quality (g) Mass ratio (%)
Methacrylic acid 125 25
Methyl methacrylate 200 40
Ethyl acrylate 75 15
Styrene 100 20
(preparation of solution b)
In as the methyl cellosolve 60g of organic solvent and the mixed liquor of toluene 40g (mass ratio 3:2) 100g, dissolving prepares " solution b " as the azoisobutyronitrile 1.2g of free radical reaction initiating agent.
(Raolical polymerizable)
In the flask that possesses stirring machine, reflux condenser, thermometer, tap funnel and nitrogen ingress pipe, drop into as the methyl cellosolve 240g of organic solvent and the mixed liquor of toluene 160g (mass ratio 3:2) 400g.The limit is blown into the nitrogen limit and stirs above-mentioned mixed liquor and heating in flask, make it be warming up to 80 ℃.
In the above-mentioned mixed liquor in flask, after dripping above-mentioned solution a in 4 hours, the solution limit in the stirred flask of limit was 80 ℃ of insulations 2 hours.Next, after dripping above-mentioned solution b in 10 minutes, the solution limit in the stirred flask of limit was 80 ℃ of insulations 3 hours in the solution in flask.And then, made the solution in the flask be warming up to 90 ℃ through 30 minutes, in 90 ℃ of insulations cooling after 2 hours, thereby obtain solution as the binder polymer of (A) composition.
In this binder polymer solution, add acetone, the mode that reaches 50 quality % according to nonvolatile component (solid constituent) prepares.The weight-average molecular weight of binder polymer is 80,000.
What explain is, weight-average molecular weight converts through the calibration curve that utilizes gel permeation chromatography (GPC) and measure and use polystyrene standard and derives.The condition of GPC is as shown in following.
The GPC condition
Pump: the L-6000 of Hitachi type ((strain) Hitachi system)
Post: following totally 3
Gelpack?GL-R420
Gelpack?GL-R430
Gelpack GL-R440 (above make trade name) for Hitachi changes into industry (strain)
Eluent: tetrahydrofuran
Measure temperature: 25 ℃
Flow: 2.05mL/ minute
Detecting device: the L-3300 of Hitachi type RI ((strain) Hitachi system)
[solution of photosensitive polymer combination]
In the solution of the binder polymer ((A) composition) that obtains, cooperate the composition shown in this table with the use level shown in the table 2 (g); In the mixed liquor that obtains; Cooperate (B) composition shown in this table and (C) composition with the use level shown in the table 3 (g), prepare the solution of the photosensitive polymer combination of embodiment 1～10 and comparative example 1～4 thus.What explain is that the use level of (A) composition shown in the table 2 is the quality (solid constituent amount) of nonvolatile component.
[table 2]
Figure BDA00001971376000211
[table 3]
Figure BDA00001971376000212
The detailed description of each composition shown in table 2 and the table 3 is following.
(light developer)
BMPS (Sumitomo refine (strain) make trade name): trisbromomethyl phenyl sulfone
LCV (hillside plot chemistry (strain) is made, trade name): LCV
(dyestuff)
MKG (Osaka organic chemistry industry (strain) is made, trade name): peacock green
((B) composition: the optical polymerism compound)
(1) compound shown in the general formula (I)
·（B-1）
9G (Xin Zhong village chemical industry (strain) is made, trade name)
Polyglycol #400 dimethylacrylate
In the general formula (I), R 1And R 2Be methyl, n=9
·（B-2）
14G (Xin Zhong village chemical industry (strain) is made, trade name)
Polyglycol #600 dimethylacrylate
In the general formula (I), R 1And R 2Be methyl, n=14
·（B-3）
23G (Xin Zhong village chemical industry (strain) is made, trade name)
Polyglycol #1000 dimethylacrylate
In the general formula (I), R 1And R 2Be methyl, n=23
(2) bisphenol-A is two (methyl) acrylate compounds (above-mentioned (B1))
·（B-4）
FA-321M (Hitachi changes into industry (strain) manufacturing, trade name)
2, two (4-(the methacryloxy five ethoxys) phenyl) propane of 2-
(3) has the compound (above-mentioned (B2)) of 1 ethene property unsaturated link
·（B-5）
FA-314A (Hitachi changes into industry (strain) manufacturing, trade name)
Nonylphenoxy TEG acrylic ester (mean value of oxygen ethylidene sum is 4)
·（B-6）
FA-318A (Hitachi changes into industry (strain) manufacturing, trade name)
Nonylphenoxy eight EDIAs (mean value of oxygen ethylidene sum is 8)
·（B-7）
FA-MECH (Hitachi Chemical Co., Ltd. makes, trade name)
γ-chloro-beta-hydroxy propyl group-β '-methylacryoyloxyethyl-phthalic ester
(4) carbamate monomer (above-mentioned (B5))
·（B-8）
UA-13 (Xin Zhong village chemical industry (strain) is made, trade name)
EO, PO modified amido formic ether dimethylacrylate
·（B-9）
UA-21 (Xin Zhong village chemical industry (strain) is made, trade name)
Three ((methyl) acryloxy TEG isocyanates) hexa-methylene isocyanuric acid ester
((C) composition: Photoepolymerizationinitiater initiater)
·（C-1）
N-1717 ((strain) ADEKA makes, trade name)
1, two (9-acridinyl) heptane of 7-
Compound (R shown in the formula (II) 3Be that carbon number is 7 alkylidene)
·（C-2）
9-PA (Nippon Steel's chemistry (strain) is made, trade name): 9-phenylacridine
Compound (R shown in the formula (III) 4Be phenyl)
·（C-3）
TR-PAD103 (Changzhou Tronly New Electronic Materials Co., Ltd. makes, trade name)
9-(3-aminomethyl phenyl) acridine
Compound (R shown in the formula (III) 4Be a tolyl)
·（C-4）
B-CIM (Hampford manufactured, trade name)
2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline
·（C-5）
9,10-dibutoxy anthracene
[photosensitive element]
The solution of the photosensitive polymer combination of embodiment 1～10 and comparative example 1～4 is coated on the polyethylene terephthalate film that thickness is 16 μ m respectively equably, and (Supreme Being people's (strain) makes; Trade name " G2-16 ") on; With dry 10 minutes of 100 ℃ hot air convection formula exsiccators, form the photo-sensitive resin that dried thickness is 38 μ m.Add through roller and to be pressed in this photo-sensitive resin laminated diaphragm (TAMAPOLY (strain) makes; Trade name " NF-13 "), thus obtain by polyethylene terephthalate film (support membrane), be formed at each photo-sensitive resin on the support membrane and be formed at embodiment 1～10 that the diaphragm on the photo-sensitive resin constitutes and the photosensitive element of comparative example 1～4.
[multilayer board]
Use has the muller (three open (strain) system) of the brush that is equivalent to #600; (Hitachi changes into industry (strain) manufacturing to the thick copper-clad laminated board of 1.6mm by glass epoxide material and Copper Foil (thickness the is 35 μ m) formation that is formed on its two sides; Goods name " MCL-E-67 ") grind on copper surface; After the washing, carry out drying through airflow.Heat this copper-clad laminated board (below be called " substrate ".) and after making it be warming up to 80 ℃, the photosensitive element lamination (range upon range of) of embodiment 1～10 and comparative example 1～4 is surperficial to the copper of substrate both sides.Lamination is to use 110 ℃ hot-rolling, carries out with 1.5m/ minute speed while remove diaphragm, so that each copper surface driving fit of the photo-sensitive resin of each photosensitive element and substrate.
[evaluation test 1: embodiment 1～10 and comparative example 1～4]
(susceptibility)
The multilayer board that obtains is placed cooling,, go up the photomask (photo tool) that driving fit has stage metraster (step tablet) at the polyethylene terephthalate film (support membrane) on multilayer board surface in the moment that reaches 23 ℃.As stage metraster, use be that concentration range is 0.00～2.00, the size of concentration stage 0.05, metraster is the size in 20mm * 187mm, each stage 41 sections stage metraster as 3mm * 12mm.Across photomask with so stage metraster and polyethylene terephthalate film photo-sensitive resin is made public.Exposure is used with semiconductor and is excited the exposure machine (Japanese Orbotech (strain) make, trade name " Paragon-9000m ") of Solid State Laser as light source, with 20mJ/cm 2Exposure carry out.
After the exposure, peel off the polyethylene terephthalate film, photo-sensitive resin is exposed,,, thereby remove unexposed portion at 30 ℃ of injection quality % aqueous sodium carbonates (development treatment) in 50 second 1 to the photo-sensitive resin that exposes from multilayer board.Like this, on the copper surface of multilayer board, form the cured film that the solidfied material by photosensitive polymer combination constitutes.The hop count of the stage metraster through the cured film that measure to obtain is estimated embodiment 1～10 and the photosensitive polymer combination of comparative example 1～4 and the susceptibility (lightsensitivity) of photosensitive element.The high more susceptibility that then means of the hop count of this stage metraster is high more.Say that the result is shown in table 4.
(adaptation)
Using above-mentionedly with the exposure machine of laser as light source, is that 5/400～200/400 (unit: line pattern μ m) is depicted on the photo-sensitive resin of above-mentioned multilayer board through direct picture with live width/relief width.The remaining stage hop count of exposure after with the development of 41 sections stage metraster of Hitachi is that 17.0 energy fluence carries out.After the exposure, carry out and the same development treatment of above-mentioned susceptibility evaluation.
The minimum value of the live width of the line pattern when not producing distortion (crawling), damaged formation through line part (exposed portion) is estimated adaptation.The more little adaptation that then means of this minimum value is good more.The result is shown in table 4.
(resolution)
Using above-mentionedly with the exposure machine of laser as light source, is that 400/5～400/200 (unit: line pattern μ m) is depicted on the photo-sensitive resin of above-mentioned multilayer board through direct picture with live width/relief width.The remaining stage hop count of exposure after with the development of 41 sections stage metraster of Hitachi is that 17.0 energy fluence carries out.After the exposure, carry out and the same development treatment of above-mentioned susceptibility evaluation.
The minimum value of the relief width through the line pattern of gap portion (unexposed portion) when removing is fully estimated resolution.The more little resolution that then means of this minimum value is good more.The result is shown in table 4.
(fissility)
Use above-mentioned with the exposure machine of laser as light source, through direct picture with the graphic depiction of 60mm * 45mm on the photo-sensitive resin of above-mentioned multilayer board.The remaining stage hop count of exposure after with the development of 41 sections stage metraster of Hitachi is that 17.0 energy fluence carries out.After the exposure, carry out and the same development treatment of above-mentioned susceptibility evaluation, acquisition is formed with the test film of the cured film of 60mm * 45mm on substrate.
After this test film at room temperature placed diel, dipping (dip) stirred with stirrer in 50 ℃ 3 quality % sodium hydrate aqueous solutions (stripper).Mensuration is from stirring beginning to peeling off the time (splitting time (second)) of removing till the cured film fully from substrate, thus the evaluation fissility.The shorter fissility that then means of splitting time is good more.The result is shown in table 4.
(lid hole reliability)
To above-mentioned copper-clad laminated board (Hitachi changes into industry (strain) system trade name MCL-E-67); With aperture making circular hole and the 3 company holes of bicker with diameter 4～6mm; Muller (three open (strain) system) with having the brush that is equivalent to #600 is removed the burr of generation, obtains the hole shown in Figure 2 number that breaks and measures and use substrate.The hole that the obtains number that breaks is measured and is heated to 80 ℃ with substrate, on its copper surface, at 120 ℃, the condition laminated embodiment 1～10 of 0.4MPa and the photosensitive element of comparative example 1～4.Lamination is to carry out while removing diaphragm, and number is measured the copper surface driving fit with substrate so that break in the photo-sensitive resin of photosensitive element and hole.Behind the lamination; Cooling holes is broken to count to measure and is used substrate; The number that breaks in the hole is measured and is reached 23 ℃ the moment with the temperature of substrate; Using above-mentionedly with the exposure machine of laser as light source, is 17.0 energy fluence p-poly-phenyl dioctyl phthalate glycol ester film (support membrane) face make public (directly picture) with the remaining stage hop count after the development of 41 sections stage metraster of Hitachi.After the exposure, at room temperature placed 15 minutes, the number that then breaks from the hole is measured with strippable substrate polyethylene terephthalate film; After the development treatment 50 seconds; Measure 3 connect holes the hole number that breaks, estimate as abnormity lid hole rupture rate, with it as lid hole reliability (%).This numerical value is more little to mean that then to cover the hole reliability high more.The result is shown in table 4.
[table 4]
Figure BDA00001971376000261
Can know that by table 4 (B-1～B-3) compare, and susceptibility is excellent with lid hole reliability by the photosensitive polymer combination of the comparative example 1～4 of conduct (B) composition with not containing the compound shown in the general formula (I) for the photosensitive polymer combination of embodiment 1～10.Especially with regard to the reliability of lid hole, comparative example 1～4 is 12～23%, is 2～6% among the relative therewith embodiment 1～10, demonstrate significantly low value, but the photosensitive polymer combination of knowledge capital invention has very excellent lid hole reliability.
[evaluation test 2: reference example 1～2]
(reference example 1)
Use the photosensitive polymer combination of embodiment 1, conditions of exposure is changed as follows, in addition, through estimating susceptibility, adaptation, resolution, fissility and lid hole reliability with embodiment 1 same step.The result is shown in table 5.
Conditions of exposure
Exposure machine: HMW-201GX (ORC (strain) makes, trade name)
Light source: high-pressure sodium lamp
Exposure when susceptibility is estimated: 40mJ/cm 2
Exposure during evaluation beyond the susceptibility: the remaining stage hop count after the development of 41 sections stage metraster of Hitachi is 23.0 energy fluence
Exposure method: mask exposure method
(reference example 2)
Use the photosensitive polymer combination of comparative example 1; Conditions of exposure is become the conditions of exposure (mask exposure method) same with reference example 1; In addition, according to estimating susceptibility, adaptation, resolution, fissility and lid hole reliability with comparative example 1 same step.The result is shown in table 5.
[table 5]
Reference example 1 Reference example 2
Susceptibility (section) 23 20.5
Adaptation (μ m) 25 20
Resolution (μ m) 45 40
Fissility (second) 60 52
Lid hole reliability (%) 20 3
As shown in table 5, use the photosensitive polymer combination of embodiment 1, carried out through mask exposure method in the past in the reference example 1 of exposure, do not obtain lid hole reliability fully.Relative therewith, as shown in table 4, use the photosensitive polymer combination of same composition, through carried out having obtained excellent lid hole reliability among the embodiment 1 of exposure as the direct picture of light source with laser.
In addition, as shown in table 5, use the photosensitive polymer combination of comparative example 1, carried out through mask exposure method in the past in the reference example 2 of exposure, obtained sufficient susceptibility and lid hole reliability.Relative therewith, as shown in table 4, use the photosensitive polymer combination of same composition, through having carried out as the direct picture of light source in the comparative example 1 of exposure with laser, aspect susceptibility and lid hole reliability, all obtain to be worth fully.
Sum up The above results; Can know: the photosensitive polymer combination that does not contain the comparative example of compound conduct (B) composition shown in the formula (I) has sufficient susceptibility and lid hole reliability when having carried out exposure through mask exposure method in the past; But when having carried out exposure, all do not have abundant value aspect susceptibility and the lid hole reliability through direct picture; Relative therewith; The photosensitive polymer combination of the present invention that contains the compound shown in the formula (I) does not have sufficient lid hole reliability when having carried out exposure through mask exposure method in the past, but when having carried out exposure through direct picture, has the susceptibility and lid hole reliability more excellent than comparative example.
Industrial applicibility
Photosensitive polymer combination of the present invention and photosensitive element have excellent lid hole reliability when having carried out exposure through direct picture, can form high meticulous resist pattern and make high meticulous printed-wiring board (PWB).
Symbol description
1: photosensitive element, 2: support membrane, 3: photo-sensitive resin, 4: diaphragm.

Claims (8)

1. photosensitive polymer combination; Its photosensitive polymer combination in the formation of the resist pattern that utilizes direct picture, using; Contain (A) binder polymer, (B) optical polymerism compound and (C) Photoepolymerizationinitiater initiater; Said (B) optical polymerism compound contains the compound shown in the formula (I)
Figure FDA00001971375900011
In the formula, R 1And R 2Represent hydrogen atom or methyl independently of one another, n representes 0～50 integer.
2. photosensitive polymer combination according to claim 1, said (B) optical polymerism compound also contains the compound shown in the formula (II),
In the formula, R 3Expression hydrogen atom or methyl, R 4The expression carbon number is 9 alkyl, and m representes 0～20 integer.
3. according to claim 1 or the described photosensitive polymer combination of claim 2, the n in the compound shown in the said general formula (I) is 4～25 integer.
4. photosensitive polymer combination according to claim 2, the m in the compound shown in the said general formula (II) are 4～8 integer.
5. according to any described photosensitive polymer combination in the claim 1～4, said (C) Photoepolymerizationinitiater initiater contains the compound shown in compound shown in the formula (III) and/or the formula (IV),
Figure FDA00001971375900013
In the formula, R 5The expression carbon number is 2～20 alkylidene, oxa-two alkylidenes or sulfo-two alkylidenes,
In the formula, R 6Expression can have substituent 1 valency aromatic series base.
6. photosensitive element, it has support membrane and is formed at any described photosensitive polymer combination in the use claim 1～5 on this support membrane and the photo-sensitive resin that forms.
7. the formation method of a resist pattern, it has:
Use any described photosensitive polymer combination in the claim 1～5 and the range upon range of operation of the photo-sensitive resin that forms in the substrate laminated;
Through direct picture said photo-sensitive resin is shone active ray with the image shape, the exposure process that exposure portion is solidified; With
Remove the unexposed portion of said photo-sensitive resin from said substrate, thereby on said substrate, form the developing procedure of the resist pattern that the solidfied material by said photosensitive polymer combination constitutes.
8. the manufacturing approach of a printed-wiring board (PWB), it comprises the substrate that is formed with resist pattern to utilizing the described method of claim 7 and carries out etching or plating.
CN201080063100.9A 2010-03-19 2010-12-14 Photosensitive resin composition and photosensitive element using same, resist pattern formation method and printed circuit board manufacturing method Active CN102754032B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2010064760 2010-03-19
JP2010-064760 2010-03-19
JP2010131906 2010-06-09
JP2010-131906 2010-06-09
PCT/JP2010/072490 WO2011114593A1 (en) 2010-03-19 2010-12-14 Photosensitive resin composition and photosensitive element using same, resist pattern formation method and printed circuit board manufacturing method

Publications (2)

Publication Number Publication Date
CN102754032A true CN102754032A (en) 2012-10-24
CN102754032B CN102754032B (en) 2015-07-15

Family

ID=44648711

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201080063100.9A Active CN102754032B (en) 2010-03-19 2010-12-14 Photosensitive resin composition and photosensitive element using same, resist pattern formation method and printed circuit board manufacturing method

Country Status (5)

Country Link
JP (1) JP5376043B2 (en)
KR (2) KR101409030B1 (en)
CN (1) CN102754032B (en)
TW (1) TWI625594B (en)
WO (1) WO2011114593A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104345559A (en) * 2013-08-09 2015-02-11 东友精细化工有限公司 Colored photosensitive resin composition, color filter and liquid crystal display having the same

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6486672B2 (en) * 2013-12-20 2019-03-20 旭化成株式会社 Photosensitive element and manufacturing method thereof
WO2015174468A1 (en) * 2014-05-13 2015-11-19 日立化成株式会社 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and process for producing printed wiring board
JP6733553B2 (en) * 2015-01-20 2020-08-05 日立化成株式会社 Photosensitive resin composition, photosensitive element, resist pattern forming method, and structure manufacturing method
US11559958B2 (en) 2015-07-23 2023-01-24 Bridgestone Americas Tire Operations, Llc Degradable foam-containing tires, related methods and kits for adding degradable foam to tires

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004184547A (en) * 2002-11-29 2004-07-02 Hitachi Chem Co Ltd Photosensitive resin composition, photosensitive element using same, method for forming resist pattern and method for manufacturing printed wiring board
CN1643451A (en) * 2002-03-12 2005-07-20 旭化成电子材料元件株式会社 Photosensitive resin composition and use thereof
JP2008094803A (en) * 2006-10-16 2008-04-24 Asahi Kasei Electronics Co Ltd Photosensitive resin composition and its laminate
JP2009042720A (en) * 2007-07-18 2009-02-26 Hitachi Chem Co Ltd Photosensitive resin composition, photosensitive element, resist pattern forming method and method for manufacturing printed circuit board
JP2009069465A (en) * 2007-09-13 2009-04-02 Asahi Kasei Electronics Co Ltd Photosensitive resin composition
WO2009154194A1 (en) * 2008-06-18 2009-12-23 日立化成工業株式会社 Photosensitive resin composition, photosensitive element wherein same is used, method for forming a resist-pattern, and method for producing a printed wiring board

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2063318A4 (en) * 2006-09-13 2010-06-23 Hitachi Chemical Co Ltd Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1643451A (en) * 2002-03-12 2005-07-20 旭化成电子材料元件株式会社 Photosensitive resin composition and use thereof
JP2004184547A (en) * 2002-11-29 2004-07-02 Hitachi Chem Co Ltd Photosensitive resin composition, photosensitive element using same, method for forming resist pattern and method for manufacturing printed wiring board
JP2008094803A (en) * 2006-10-16 2008-04-24 Asahi Kasei Electronics Co Ltd Photosensitive resin composition and its laminate
JP2009042720A (en) * 2007-07-18 2009-02-26 Hitachi Chem Co Ltd Photosensitive resin composition, photosensitive element, resist pattern forming method and method for manufacturing printed circuit board
JP2009069465A (en) * 2007-09-13 2009-04-02 Asahi Kasei Electronics Co Ltd Photosensitive resin composition
WO2009154194A1 (en) * 2008-06-18 2009-12-23 日立化成工業株式会社 Photosensitive resin composition, photosensitive element wherein same is used, method for forming a resist-pattern, and method for producing a printed wiring board

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104345559A (en) * 2013-08-09 2015-02-11 东友精细化工有限公司 Colored photosensitive resin composition, color filter and liquid crystal display having the same
CN104345559B (en) * 2013-08-09 2018-10-19 东友精细化工有限公司 Photosensitive composition and colored filter and liquid crystal display with it

Also Published As

Publication number Publication date
KR20120139790A (en) 2012-12-27
JP5376043B2 (en) 2013-12-25
KR20140009600A (en) 2014-01-22
KR101409030B1 (en) 2014-06-18
KR101775206B1 (en) 2017-09-05
WO2011114593A1 (en) 2011-09-22
CN102754032B (en) 2015-07-15
TWI625594B (en) 2018-06-01
TW201207554A (en) 2012-02-16
JPWO2011114593A1 (en) 2013-06-27

Similar Documents

Publication Publication Date Title
CN102393605B (en) Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board
CN102662306B (en) The manufacture method of photosensitive element, corrosion-resisting pattern formation method and printed circuit board (PCB)
CN102272676B (en) Photosensitive resin composition, and photosensitive element, resist pattern formation method and printed circuit board production method each utilizing same
CN102375341B (en) The manufacture method of photosensitive polymer combination, element, resist figure and lead frame, printed-wiring board (PWB) and manufacture method thereof
CN102395924B (en) Photosensitive resin composition, photosensitive element utilizing the composition, method for formation of resist pattern, and process for production of printed circuit board
CN103339568A (en) Photosensitive resin composition, photosensitive element, method for producing resist pattern, and method for manufacturing printed wiring board
CN102007451A (en) Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board
CN103543608A (en) Photosensitive resin composition, and photosensitive element, resist pattern formation method and printed circuit board production method each utilizing same
CN105393171A (en) Photosensitive resin composition for projection exposure, photosensitive element, method for forming resist pattern, process for producing printed wiring board and process for producing lead frame
CN102341753B (en) Photosensitive resin composition, and photosensitive element, resist pattern formation method and printed circuit board production method each utilizing same
CN101981502A (en) Photosensitive resin composition, photosensitive element, method of forming resist pattern and method of producing printed wiring board
CN103221887A (en) Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board
CN102037406A (en) Photosensitive resin composition, photosensitive element, resist pattern manufacturing method, and printed circuit board manufacturing method
CN102067037B (en) Photosensitive resin composition, photosensitive element wherein same is used, method for forming a resist-pattern, and method for producing a printed wiring board
KR102171606B1 (en) Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board
CN101558356B (en) Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board
CN102754032B (en) Photosensitive resin composition and photosensitive element using same, resist pattern formation method and printed circuit board manufacturing method
CN101410755B (en) Photosensitive resin composition, photosensitive element using same, method for forming resist pattern, and method for producing printed wiring board
CN103064254A (en) Photosensitive resin compound, photosensitive component, formation method of resist pattern, and manufacturing method of printed circuit board
CN104040431A (en) Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board
CN102854750B (en) Photosensitive resin composition, photosensitive element, method for forming resist pattern, method for producing lead frame, and method for producing printed wiring board
CN102375335B (en) Manufacturing method of resin composition, photosensitive element, resist pattern and circuit board
JP2016224161A (en) Method for forming resist pattern, method for manufacturing printed wiring board and photosensitive element
CN102981357A (en) Photosensitive resin composition, and photosensitive element, and resist pattern formation method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C53 Correction of patent of invention or patent application
CB02 Change of applicant information

Address after: Japan

Applicant after: HITACHI CHEMICAL Co.,Ltd.

Address before: Tokyo, Japan

Applicant before: HITACHI CHEMICAL Co.,Ltd.

COR Change of bibliographic data

Free format text: CORRECT: APPLICANT; FROM: HITACHI CHEMICAL CO. LTD. TO: HITACHI CHEMICAL CO., LTD.

Free format text: CORRECT: ADDRESS; FROM:

C14 Grant of patent or utility model
GR01 Patent grant
CP01 Change in the name or title of a patent holder

Address after: Japan

Patentee after: Lishennoco Co.,Ltd.

Address before: Japan

Patentee before: HITACHI CHEMICAL Co.,Ltd.

CP01 Change in the name or title of a patent holder